Alkylation of trihydric phenols



Patented Nov 23, 1937 PATENT OFFICE.

2,099,738 ALKYLATION OF TRIHYDRIC PHENOLS Vladimir Ipatiefl, Chicago, Ill.. assignor to Universal Oil Products Company, Chicago, 111.. a corporation of Delaware No Drawing. Application June 30, 1934, Serial No. 733,335. Renewed May 26, 1936 8 Claims. (Cl. 260-154) This application is a continuation in part of my co-pending application, Serial No. 656,373, filed Feb. 11, 1933.

This invention relates to the manufacture of hydrocarbon derivatives and refers more particularly to the manufacture of compounds of a ring character containing both alkyl and bydroxyl groups.-

, More specifically the invention has reference 10 to a process 'for manufacturing alkyl derivatives of the classf; of compounds known generally as phenols which comprises either mono or'poly nuclear ring compounds containing hydroxyl groups.

The phenols constitute an important class of chemical compounds which occur in varying amounts in the products obtained when distilling various carbonaceous materials such as coal, shale, lignite, peat, wood, etc. Many of these individual compounds and the commercial mixtures obtained from primary distillation products have value as germicides and insecticides and as base products for the manufacture of more complicated substances such as, for example, various resinous condensation products produced by reacting phenols and aldehydes.

The following table gives a list of some of the mono nuclear phenols of a mono, diand trihydric character.

Phenols Formula ag? Boiling po t I OH Hydroquinone (p...) 1w 0. as o.

Tri-hydric. on 133' 0. Dec. at 293 0| P o allol Oxyhydro qui- 140.6 0.

none

Phloroglucinol 218 C. Subl. doc.

HO OH The invention further comprises the manufacture of derivatives of polynuclear phenols which are characterized by such compounds as alpha naphthol with a melting point of 94 C. and a boiling point of 279 C. and beta naphthol with a melting point of 122 C. and a boiling point of 285.5 C.

In one specific embodiment the present inventioncomprises the production of alkyl derivatives of tri-hydric phenolic compounds by treatment of the same with oleilns in the presence of phosphoric acid.

I have discovered that the alkylation of phenols may be accomplished with greatly improved emciency by using phosphoric acid; instead of such previously used condensing agents assulphuric acid and heavy metal chlorides including aluminum and zinc chlorides. When using such reagents the reactions of alkylation are attended by various types of undesirable side reactions which decrease the yield of desired products. For example, with sulphuric acid of sumcient concentration to produce material yields of alkylated derivatives of phenols there is always anundesirable amount of sulp honat ion and tar formation. With aluminum chloride and similar compounds there is also a considerable loss on account of the formation of addition compounds of an intermediate character which gradually resinify to produce heavy residues of no value.

In contrast to the difiiculties experienced previously the use of phosphoric acid (and other suitable acids of phosphorus) according to the process of the present invention minimizes the side reactions and produces high yields of compounds of the desired character, to wit, phenols with ring hydrogen atoms substituted by alkyl residues. While the commoner acids of phosphorus such as the well known ortho-phosphoric acid and ortho-phosphorous acid are generally preferable on account of their ready availability Table II Acids Formulas M. P. C. Dec. C.

Hyggphosphorous HIPO: 26. 5 Above m. p.

0 g 110ml HIPOs, PaOsBHsO 70.0 200 Pyrop p rous HAPIOI, PsOaZHrO 38.0 130 fiypophosphorlc HiPiOl, P104.2H|O 55. 0 70 otaphosphorie H aHzo Sublimes Pyrophosphoric 114F101, P;O;.2Hr0 61 Orthophosphoric H|P0|, 150 ;3Hz0 38.6 H s 8 In producing alkyl derivatives of phenols according to.the process of the present invention the exact mode of procedure will vary with the nature of the constituents. A very simple procedure in the case of tri-hydric phenols which are fiuid at, moderately elevated temperatures and olefins which are gaseous or readily vaporized, consists in passing the olefin vapor into a suspension of phosphoric acid in the phenol, intimate contacting of the reacting compounds with acid catalyst being assured by either vigorous mechanical agitation or the forcible in- Jection of the vapors in the form of fine bubbles.

Where, the phenol is substantially non-volatile at temperatures slightly above its melting point it will usually be unnecessary to employ pressure higher than ordinary atmospheric, though superatmospheric pressures may be employed if economy-is gained thereby or the rate of reaction is increased. This type of operation is essentially a batchprocedure, the introduction of the olefin vapor being continued until the desired degree of allwlation is effected, at which time the stream of vapor is stopped and the acid catalyst allowed to settle, the desired product being run off into suitable storage while the catalyst is subiected to any suitable necessary purifying or regenerating steps before being further used.

An effective method of contacting which may be applied to continuous operation consists .in forcibly injecting olefin vapors, acidcatalyst and fluid phenol into mixing devices positioned inside the top of filled columns, the emulsion produced being allowed to trickle downwardly over the filling material to complete the initiated reactions, all reaction products being withdrawn from the bottom of the tower and separated as before.

The main course of the reactions which occur when phenols are treated with olefins in the presence of acids of phosphorus is illustrated by the following equations:

v I CsH1 0.1301! 0,11. i cm.

(Phenol) (Propylene) (Iso-propylphenol) OH 01H C|H| CzHr 'g C|H OH CH CH: (Grssol) (Ethylene) (Methyl-ethyl phenol) C3111 OH com cs CaHc 3 0.11 9H OH (Progailol) (Propylene) (Iso-propyl pyrogallol) Reactionsof the above character may be made to occur in predominating amounts, frequently 95% of the phenol being thus converted.

The process may be employed to effect the reaction between chemical individuals comprising phenols on the one hand and olefins on the other or itmay be employed to produce mixtures of allrvlatedproducts by using either phenolic mixtures or olefinic mixtures or both. For example, a mixture of alkylated derivatives may be produced by reacting the tar acids separated from various crude tars by caustic alkali (and later acidification) with olefin-containing gas mixtures such for example as those encountered in oil cracking processes either aimed primarily at the production of gasoline or of. fuel gas. Mixtures thus produced may find application as germicidal, insecticidal or disinfecting material or may in some cases be employed-as inhibitors or antioxidants for preventing the formation of gummy and resinous polymers from the olefins contained in such materials as cracked gasoline or comnercial fuel gases. It ,is a matter of frequent observation though not always a general rule that the presence of alkyl substituting groups in phenolscorresponds to increased: inhibiting value. For example, phenol itself has a relatively low value for preventing the deterioration of cracked gasoline upon storage whereas a mixture of cresols commonly known as tri-cresol has greatly increased value in this respect. The substitution of alkyl residues of higher molecular weight than the methyl residue, for example, the butyl residue, has been observed to still further increase the value as inhibitors of the base plienolic substances The following examples illustrate results obtainable in alkylatingvarious phenols at atmospheric pressure, though it is understood that these are merely illustrative and can .be supplemented by a number of further instances.

Example I I A mixture of '70 parts by weight of phenol and 30 parts by weight of 89% phosphoric acid was vigorously agitated and subjected to treatment with propylene gas at temperatures of from to C. and atmospheric pressure until approxi There was substantially no polymer or tar formation and the products of the reaction were completely soluble in 15% aqueous caustic soda. The distillation test or the product was as follows:

Percent Fraction 85-205 C 6 Fraction 205-220 C 43 Fraction 220-230 C 28 Fraction 230242 C 11 Higher boiling fraction Example 2 upon a Pennsylvania cracked gasoline which had previously been clay. treated and showed an induction period of 45 minutes by the oxygen bomb test. The same gasoline when subjected to the oxygen bomb test after the addition of 0.01% by weight of pyrogallol had an induction period of 1005 minutes and the gasoline with added inhibitor showed a 28 color by Saybolt. The increased inhibiting value of the alkylated product is shown by the fact that a sample of the same Pennsylvania cracked gasoline to which was added 0.005% by weight of the alkylated phenol showed an induction period of 850 minutes by the oxygen bomb test while the gasoline with the inhibitor added showed a 30 color by Saybolt.

The foregoing specification and numerical data. adduced in support of the operability and utility of the invention are sufficient for their respective purposes but are not to be considered in a narrow sense as imposing undue limitations on the generally broad scope of the invention.

I claim as my invention:

1. A process for the treatment of tri-hydric phenols to produce alkyl derivatives thereof which comprises, subjecting the said tri-hydric phenols to the action of an olefinic hydrocarbon in the presence of an acid of phosphorus.

2. A process for the treatment of pyrogallol to produce alkyl derivatives thereof which comprises, subjecting the said pyrogallol to the action of an olefinic hydrocarbon in the presence of an acid of phosphorus.

3. A process for the treatment of hydroxyhydroquinone to produce alkyl derivatives thereof which comprises, subjecting the said hydroxyhydroquinone to the action of an olefinic hydrocarbon inthe presence of an acid of phosphorus.

4. A process for the treatment of phloroglucinol to produce alkyl derivatives thereof which cornprises, subjecting the said phloroglucinol to the action of an olefinic hydrocarbon in the presence of an acid of phosphorus.

5. A method for producing alkylated tri-hydric phenols which comprises reacting a tri-hydric phenol with an olefin hydrocarbon in the presence or a phosphoric acid.

6. A method for producing alkylated tri-hydric phenols which comprises reacting a tri-hydric phenol with a gaseous olefin hydrocarbon in the presence of a phosphoric acid.

VLADIMIR IPATIEFF. 

